Detergent compositions based on mixtures of alpha-olefin sulfonates and dimer olefin sulfonates



United States Patent 3,544,475 DETERGENT COMPOSITIONS BASED ON MIX-TURES OF ALPHA-OLEFIN SULFONATES AND DIMER OLEFIN SULFONATES ShinichiTomiyama, Ichikawa-shi, Akira Mori and Masuzo Nagayama, Tokyo, MasayasuTakao, Funabashi-shi, and Hitoshi Sekiguchi, Tokyo, Japan, assignors toLion at & Oil Co., Ltd., Tokyo, Japan, a corporation of apan No Drawing.Filed Sept. 20, 1968, Ser. No. 761,281 Claims priority, applicationJapan, Sept. 29, 1967, 42/ 62,301 Int. Cl. Clld 1/14, 3/65 U.S. Cl.252-161 1 Claim ABSTRACT OF THE DISCLOSURE A powdered or granulardetergent composition, su perior in controlled suds and free-flowcharacteritsics, containing the active ingredients consisting of 50 to97 percent by weight of sodium a-olefine sulfonates having from about 12to about 20 carbon atoms, and 3 to 50 percent by weight of sodiumsulfonates of the compounds having a general formula of C=CH2 wherein Rand R are alkyl groups and the total carbon atoms are between about toabout is disclosed.

BACKGROUND OF THE INVENTION Field of the invention The present inventionrelates to a powdered or granular detergent composition which comprisesessentially of a-olefine sulfonates having substantially from 12 to 20carbon atoms and sulfonates of the compounds having a general formula ofwherein R and R' are alkyl groups and the total carbon atoms aresubstantially from 10 to 20.

Description of the prior art The detergents which mainly composed ofalkylbenzene sulfonate (ABS) are used as household products, because ofits markedly superior foaming power and detergency. ABS, however, is noteasily degraded by microorganisms, has high foaming power at lowconcentration, is highly permeable, and has some irritation to skin.

From these points, the detergents which have excellent quality of ABSand have not its defects are desired, and a-olefine sulfonate has beennoticed. The a-olefine sulfonate are usually made by sulfonation ofa-olefine mixtures having 12-20 carbon atoms, which may contain a smallquantity of hydrocarbons other than a-olefins, using gaseous sulfurtrioxide, followed by neutralization and hydrolysis of the reactionproducts. The a.-olefine sulfonates have excellent detergency, free-flowproperty in granular form and biodegradability. But in the presence ofoily soils, they are somewhat inferior in detergency than ABS and theirfoaming power at low concentrations is as high as ABS, that is, theyhave not good controlled suds property. Any substances which improve thecontrolled-suds property of m-olefine sulfonates have been unknown, soa-olefine sulfonates should be very 3,544,475 Patented Dec. 1, 1970excellent compounds for household detergents when these substances ofthe above mentioned could be discovered.

Other than the said a-olefines, there are vinylidene compounds havingthe general formula of so-called dimer olefines, which are produced fromethylene, propylene and so on. We had interest so much in the propertiesof the sulfonates of these compounds having 1020 carbon atoms, and so weprepared their sulfonates and tested their properties. Of course, suchdimer olefine sulfonates are new compounds and their properties havebeen unknown.

As the results of our tests, it became clear that the sulfonates of thecompounds having a general formula of (total carbon number=1020)markedly improved the controlled suds property without lowering theproperties of free-flowing and detergency, when they were added toot-olefine sulfonates in the definite amount, and their detergency inthe presence of oily soils were better than a-olefine sulfonates only.

SUMMARY OF THE INVENTION It is an object of the present invention toprovide a granular detergent composition superior in controlled suds andfree-flow characteristics, containing active ingredients consisting of50% to 97%, preferably 70% to of m-olefine sulfonates having about 12 to20 carbon atoms and 3% to 50%, preferably 5% to 30%, of sulfonates ofthe compounds having a general formula of wherein R and R are alkylgroups and have about 10 to 20 carbon atoms. This detergent compositionmay also contain usual detergent builders such as polyphosphates,carbonates and so on, and, if needed, may contain a small amount ofother surfactants or additives.

a-Olefines used as a raw material for wolefine sulfonates in the presentinvention, may be the one having single chain length carbon number, suchas fractionated product of a-olefines made by Ziegler process, or amixture having different carbon chains such as waxcracking olefines.Usually (it-olefines are commercially sulfonated with gaseous sulfurtrioxide diluted with inert gas by using thin-film sulfonator, and thereaction products are neutralized with caustic alkali (usually sodiumhydroxide) and then hydrolyzed to obtain sulfonates.

In the present invention, the said dimer olefines may be derived eitherway from single carbon olefine or different carbon olefines, but thesaid dimer olefine should contain above vinylidene compounds as itsmajor component. To sulfonate these compounds both batch and continuousprocess can be used, but it is commerically desirable to use the samemethod as in the case of aolefine sulfonates, because a large amount ofdisulfonates and some by-products are produced in the batch process.

3 DESCRIPTION OF THE PREFERRED EMBODIMENTS Example 1 Heavy duty granulardetergent: Wt. percent (1) Na-a-olefine sulfonate (made from wax-1cracking u-olefine having 15-18 carbon atoms) (2) Na dimer olefinesulfonate (made from dimer olefine having 16 carbon atoms) (3) Sodiumtripolyphosphate 4 (4) Na silicate 3 (5) Sodium carbonate 5 (6) CMC 2(7) Sodium sulfate Balance Of the above compositions, components 1 and 2were varied as described in the next table. The detergent products werespray-dried by a disc-type dryer, and tested 4 EXAMPLE 2 Light dutygranular detergent:

(l) Na-u-olefine sulfonate (made from Ziegler a-olefine having mainly 16car- Wt. percent bon atoms) 20 (2) Na-dimer olefine sulfonate (made fromdimer olefine having 1216 carbon atoms) (3) Na-lauryl sulfate 5 (4)Sodium sulfate Balance Of the above compositions, components 1 and 2were varied as Example 1 described before and tested the foam height andfree-flow property and further the detergency in the presence of oilysoils. To test the detergency, every dish was soiled with 2.5 g. ofshortening oil, then washed with the detergent solution (0.25% Thenumber of washed dishes until the area covered with the foam decreasedto 50% of the surface was described below.

N orn .-consideration.

1. Dimer olefine sultonate has excellent detergeney to oily soils.

2. Controlled sudsing property is nearly equal with increase of DOS(dimer olefine sulfonate) content.

3. Free-flow property is as similar as in the case of Example 1.

the foam height at the concentration of 0.2% and 0.02% and free-flowproperties. I

The test methods used areas follows:

(1) Foaming height was measured according to Ross Miles method, at C.,after 1 min.

(2) Free-flow test:

(a) Preparation of the test samples.The detergents to be tested werepacked in the ordinal carton, and kept in a weathering room adjusted to85% relative humidity and C. for 24 hours.

(b) Measuring of free-flowing.-After opening the top of the carton, thedetergents were flowed down through the out-let by gravity or slightshock with inclining the carton, and then the condition of flowingdetergent was observed.

(c) Evaluation of the flowing condition.

Score Condition Flow continuously. 8-- Flow well, but stop twice orthree times. 6- Flow intermittently. 5 Not flow down, but after oneshock full,

detergent flow down by gravity.

Foam height,

Na-a- Na-dimer (mm.) Freesuli'onate sulfonate 0. 2% 0. 02% score 1Control- 10o o 185 72 10 Sample No.:

I See table below:

NorE.Consideration.

1. Foam height in all the samples were nearly equal at concentration of0.2%, but at 0.02% the foam height of the detergent containing Nudlmerolefine sulionate decreased.

2. Free-flow property didnt change when the content of dimer olefinesulfonate were up to 80%, but tended to be interior with increasingcontent, so the amount can be added may be less than 50%.

We claim:

1. A detergent composition consisting essentially of from 50 to 97percent by weight of sodium u-olefine sulfonates having from about 12 to20 carbon atoms and from 3 to 50 percent by weight of sodium sulfonatesof compounds of the formula wherein R and R' are alkyl groups and thetotal carbon atoms are from about 10 to 20.

References Cited UNITED STATES PATENTS 3,444,087 5/ 1969 Eccles et a1.252-138 2,695,327 11/1954 Ziegler et al 260-68315 LEON D. ROSDOL,Primary Examiner D. L. ALBRECHT, Assistant Examiner US. Cl. X.R.

